CN106345324A - Method for preparing hybridized ion exchange membrane - Google Patents
Method for preparing hybridized ion exchange membrane Download PDFInfo
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- CN106345324A CN106345324A CN201610776238.2A CN201610776238A CN106345324A CN 106345324 A CN106345324 A CN 106345324A CN 201610776238 A CN201610776238 A CN 201610776238A CN 106345324 A CN106345324 A CN 106345324A
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- exchange membrane
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
- B01D71/82—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74 characterised by the presence of specified groups, e.g. introduced by chemical after-treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0011—Casting solutions therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/38—Esters containing sulfur
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/36—Introduction of specific chemical groups
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/24—Mechanical properties, e.g. strength
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/30—Chemical resistance
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/42—Ion-exchange membranes
Abstract
The invention discloses a method for preparing a hybridized ion exchange membrane. The method comprises the following steps: (1) dissolving one or more organic silicon monomers containing carbon-carbon double bonds or multiple ionic monomers containing carbon-carbon double bonds into an organic solvent so as to form a monomer solution; (2) feeding the monomer solution into a porous polymer substrate, and enabling free radicals to polymerize to form a complex inside the substrate; (3) performing thermal treatment on the complex to promote a sol-gel reaction, thereby finally forming the hybridized ion exchange membrane. The hybridized ion exchange membrane prepared by using the method has relatively low resistance, and is good in temperature resistance, acid and base resistance, organic solvent resistance and flexibility.
Description
Technical field
The invention belongs to technical field of membrane is and in particular to a kind of organic silicon monomer of use carbon-carbon double bonds and carbon-carbon double bonds
Ion monomer (ion monomer refers to monomer containing ion exchanging function group or containing the base that can be converted into ion exchanging function group
The monomer of group) method that hydridization ion exchange membrane is prepared in combined polymerization, and sol gel reaction is promoted by heat treatment.
Background technology
Juda and mcrac, winger of nineteen fifty-three rohm company from nineteen fifty U.S. ionics company etc. sends out clear property
Since ion exchange membrane that can be excellent, ion exchange membrane and its correlation technique have obtained rapid development.The sixties in 20th century, day
This Asahi Kasei Corporation achieves the industrialization with monovalent ion selective membrane from preparing salt by working up seawater；20 century 70s, du pont is public
Department have developed the highly stable perfluorinated sulfonic acid of chemistry and carboxylic acid composite membrane-cation exchange membrane (nafion series), realizes
Ion exchange membrane is in the large-scale application of chloric alkali electrolysis industry and energy storage system (fuel cell).China is to ion exchange membrane
Research work start from 1958, be at that time ion exchange resin is milled into powder after, be processed into ion exchange membrane.1966
After year, China enters Rapid development stage to the research and development of ion exchange membrane, the researching and developing and throwing in succession of all kinds of ion exchange membranees
Enter to produce.
Ion exchange membrane because its excellent separation selectivity be widely used in chemical industry, water process, environmental conservation, food,
The fields such as hydrometallurgy.According to its in the application separate object different from purpose, ion exchange membrane is mainly used in electrodialysis, diffusion
Dialysis and donnan(Donnan) dialysis.
Ion exchange membrane and electrodialyzer, can be used for removing the salinity (desalinating) of aqueous solution or the salinity of concentrated aqueous solution
(salt manufacturing), specifically applies the material desalination including in various chemical industry/food/medicine production, brackish water desalination, natural water
Purification, industrial waste water purifying, small-scale desalinization, sea water or salt salt manufacturing etc..In such applications, electroosmose process has it
The incomparable advantage of its method.With ion exchange membrane assembling desalinization electrodialysis plant have small volume, little power consumption and
Easy to operate the features such as, it is arranged on seagoing vessel and can improve endurance, be arranged on island and can solve the problem that resident living water is asked
Topic etc..
Diffusion dialysis process is to make the solute in solution pass through film to low concentration from high concentration side by ion exchange membrane
The process of side migration.Diffusion dialysis is reached to the selective penetrated property of acid/salt or alkali/salt using seperation film and separates purpose, can
The resource realizing the acid/base in waste liquid recycles, and operating cost is extremely low, changes mistake existing for traditional processing method
Journey complexity, operating cost height, high energy consumption, investment is big, the shortcomings of easily cause secondary pollution.
Donnan dialysis process is the selective penetrated property energy using film for the counter ion in solution, is not needing DC electric field
Under the conditions of, in the both sides phase counterdiffusion of ion exchange membrane, and realize the separation of counter ion.In water process, donnan dialysis
Journey is mainly used in two aspects: one is water miscible contaminant ion to be carried out separate removing, such as fluoride, perchlorate,
Heavy metal ion etc.；Two is that the micro heavy concentration in water is tested and analyzed.
The core of membrane separation technique is ion exchange membrane.The function of film depends primarily on the property of membrane material and the knot of film
Structure.Traditional membrane material has organic polymer and inorganic ceramic material.But organic film material exists, and mechanical strength is bad, chemically stable
Property difference and non-refractory, soda acid and the shortcomings of organic solvent, inorganic material film has that species is few, material is more crisp, film forming procedure becomes
This higher and difficult to form is continuous and the shortcomings of zero defect structure.Hybrid inorganic-organic is exactly by different active forces such as
High forces (ionic bond, covalent bond) or weak force (hydrogen bond), inorganic component are combined with organic material, thus obtaining one
Plant new seperation film.In inorganic component, a class is simple inorganic powder material, such as titanium dioxide osmanthus, titanium dioxide, three oxidations
Aluminum etc., in addition a class is the precursor that organosilicon, organic titanium, organo-aluminium etc. can continue to react.In most research work
In, in organic-inorganic hybrid films, organic faciess are usually by Kynoar, pi, polyvinyl alcohol, shitosan, poly- second two
The high polymer of the macromole such as alcohol, polyphenyl acid, polymethyl methacrylate is as the matrix of film.Hydridization ion exchange membrane has concurrently organic
Membrane material and the advantage of inorganic material film, the heat stability of inorganic component energy reinforcing membrane and mechanical performance, organic component then helps
In the machinability, pliability and the chemical stability that improve film.Therefore hydridization ion exchange membrane becomes new film field, has
It is widely applied prospect.At present hydridization ion exchange membrane be mainly used in fuel cell, diffusion dialysis, electrodialysis, infiltration evaporation,
The aspect such as electro chemical analysis and sensor.
The preparation method of hydridization ion exchange membrane includes direct blending, situ aggregation method, layer-by-layer, interts
Method, phase inversion, thermojet sedimentation and sol-gel process.Wherein sol-gel process is that to prepare inoranic membrane in the early time the most frequently used
Method, the condition that the method requires is gentleer, and reaction can be carried out at a lower temperature.If reaction system or raw material are made
After conversion, the preparation of hybrid organic-inorganic film can also adopt sol-gel process, and through continuous research and development, should
Method has become as the main method of preparation hybridized film at present.Sol-gel process possesses advantages below: (1) is easy to operate, at present
Technique is close to ripe.(2) sol-gel process can operate at a lower temperature, and the organic principle being capable of in film is not broken
Bad, this characteristic is quite important for the film containing bioactive species in preparing raw material.(3) sol-gel process masking is permissible
Carry out selection raw material and its proportioning of motility as needed, this is because the initial period of sol gel reaction, system viscosity
Less, each component can be sufficiently mixed, thus the film with heterogeneity and function is obtained, and each component dispersion in film is all
Even.
A kind of organic/inorganic hybridisation strong alkalinity is described cloudy in the Chinese patent document of Patent No. 200810064728.5
Ion exchange membrane and preparation method thereof.Specific implementation method is to weigh Kynoar, polyether-ether-ketone, diethyl by weight percentage
Alkenyl benzene, ethyl styrene, dimethyl phthalate, nano-aluminium oxide granule and organic solvent ultrasonic mixing, add
Other compositions prepare casting solution, casting solution masking, put into dipping in hcl solution by after film immersion, rinsing, self-cleaning obtains final product organic
Inorganic hybridisation strong alkalinity anion exchange membrane.Describe one kind in the Chinese patent document of Patent No. 200810064727.0 to receive
Organic inorganic hybridization cation exchange membrane of rice grain filling and preparation method thereof, specific implementation method is to hand over above-mentioned anion
The amination step changing film is changed to sulfonation procedure.Above-mentioned film-forming method is first first to be polymerized after masking with glycidyl methacrylate
Amination obtains anion exchange membrane or sulfonation obtains cation exchange membrane.Need reagent type more in preparation process, operated
Journey is loaded down with trivial details, and the persistent period is longer.Lack covalently cross-linked, less stable in film simultaneously.
Describe in the Chinese patent document of Patent No. 201310197376.1 a kind of inorganic/organic polymer hybrid from
Proton exchange and preparation method.Specific implementation method is as basement membrane, dioxide composite in its hole using politef
Silicon or titanium dioxide or the two mixture, form inorganic/organic hybrid ion exchange membrane.The hydridization ion exchange of preparation
Film has very high ionic conductivity and oxidation-reduction resistance.But lack covalent bond in the hydridization ion exchange membrane of the method preparation
Crosslinking, membrane stability is not enough, and this film is only applicable in zinc-bromine flow battery.
A kind of coating liquid, organic inorganic hybridization is described in the Chinese patent document of Patent No. 201210057066.5
Cation exchange membrane and preparation method thereof.Specific implementation method is with the monomer a containing sodium benzenesulfonate group, group containing alkoxyl silicone
Monomer b, solvent c and initiator d hybrid reaction after remove excess of solvent many silicon cross-linking agent is obtained, then many silicon cross-linking agent is added
Enter and obtain coating liquid in the poly-vinyl alcohol solution of dissolving, then film obtains hybrid cation-exchange membranes.The method obtains hydridization
Cation exchange membrane, has the advantages that degree of cross linking height, transparent and homogeneous, satisfactory mechanical property, anti-Swelling Capacity and heat stability are high,
Can be applicable to field of alkali recovery.But need in many silicon cross-linking agent preparation process through excess of solvent is distilled off, not only waste molten
Agent, and complex operation.The hybrid cation-exchange membranes moisture content simultaneously prepared is higher, and resistance is larger, is only applicable to diffusion and oozes
Analysis process, is not suitable for electrodialytic process.
Content of the invention
It is an object of the invention to provide a kind of preparation method of hydridization ion exchange membrane.
In order to realize foregoing invention purpose, the preparation method of hydridization ion exchange membrane provided by the present invention includes following step
Rapid: the ion monomer of the organic silicon monomer of one or more carbon-carbon double bonds and one or more carbon-carbon double bonds has been dissolved in
Form monomer solution in machine solvent, so that monomer solution is entered in porous polymer matrix and make radical polymerization shape in base material
Become complex, complex promotes sol gel reaction to ultimately form hydridization ion exchange membrane through heat treatment.
Described ion monomer refers to monomer containing ion exchanging function group or containing can be converted into ion exchanging function group
The monomer of group；Described ion monomer is the negatively charged monomer of fixed group, including acrylic acid, methacrylic acid, methyl-prop
Olefin(e) acid 2- sulphur ethyl ester, methacrylic acid 3- sulphur propyl ester, 2- acrylamide-2-methyl propane sulfonic, methacrylic acid sulfonation shrink are sweet
Grease, styrene sulfonate or 1- allyloxy -2- hydroxyphenyl sulfonate, are used for preparing cation exchange membrane；Described ion list
Body is the positively charged monomer of fixed group, including MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, 3- acrylamide propyl three
Ammonio methacrylate, vinylbenzyltrimethyl ammonium chloride, vinyl benzyl chloride or 1- vinyl imidazole, for preparing anion exchange
Film.
Containing the neutral monomer of one or two or more kinds in described monomer solution, described neutral monomer includes methacrylic acid
Methyl ester, ethyl methacrylate, propyl methacrylate, acrylic acid methyl ester., ethyl acrylate, propyl acrylate, acrylic acid hydroxyl
Methyl ester, 2-(Acryloyloxy)ethanol, Hydroxypropyl acrylate, hydroxy methyl methacrylate, hydroxyethyl methylacrylate or methacrylic acid
Hydroxypropyl acrylate；Described neutral monomer is 0-0.5:1 with the mol ratio of ion monomer.
Containing the cross-linking agent of one or two or more kinds in described monomer solution, described cross-linking agent refers to that molecular structure at least contains
The Organic substance of two carbon-carbon double bonds, including Ethylene glycol dimethacrylate, divinylbenzene, dimethacrylate 1,3- fourth two
Alcohol ester, diacrylate 1,3 butylene glycol ester, dimethacrylate 1,4- butanediol ester, diacrylate 1,4- butanediol ester, dipropyl
Olefin(e) acid 1,6-HD ester, pentaerythritol triacrylate, dimethacrylate TEG ester, divinylbenzene, three hydroxyl first
Base propane triacrylate, isophorone diisocyanate, glycidyl methacrylate or trimethylol propane trimethyl
Acrylate；Described cross-linking agent is 0-0.5:1 with the mol ratio of ion monomer.
Described monomer solution contains the small molecule organic compound of water or hydroxyl, the small molecule organic compound of described hydroxyl
Including methanol, ethanol, propanol, butanol or isobutanol；The small molecule organic compound of described water or hydroxyl and the matter of ion monomer
Amount ratio is 0-1:1.
Described organic silicon monomer is silane coupler, including γ-(methacryloxypropyl) propyl trimethoxy silicane, ethylene
Base trichlorosilane, VTES or vinyltrimethoxy silane and vinyl three (b- methoxy ethoxy) silicon
Alkane；Described organic silicon monomer is 0.1-1:1 with the mol ratio of ion monomer.
Described organic solvent includes but is not limited to n- methyl pyrrolidone, n, n- dimethylformamide, n, n- dimethyl second
Amide or dimethyl sulfoxide；Described machine solvent is 0-2:1 with the mass ratio of ion monomer.
Described radical polymerization is polymerized by base by what the initiator that is added in monomer solution caused, or by heat, light,
The radical polymerization that radiation, plasma or microwave cause.
Described initiator includes benzoyl peroxide, Ammonium persulfate., 2,2- azodiisobutyronitrile, 2,2- azo two (2- first
Base third amidine) dihydrochloride, 2,2- azo two [2- (2- imidazoline -2- base) propane] dihydrochloride, 2,2- azo two [2- (22- miaow
Oxazoline -2- base) propane] or dimethyl 2,2- azo two (2 Methylpropionic acid ester)；Described initiator and the mol ratio of ion monomer
For 0.005-0.1:1.
Described porous substrate is various material non-woven fabrics or microporous filter membrane；Described heat treatment refers to heat complex,
Promote the sol gel reaction of siloxane group, ultimately form hydridization ion exchange membrane.
The present invention adds neutral monomer in monomer solution, is to adjust hydrophilic, improving the mechanical performance of film；Add
Water or hydroxyl small molecule organic compound, are to promote sol gel reaction.
The invention has the advantages that providing ionic group for membrane material after the polymerization of organic ion monomer, and organosilicon
Inorganic si--o si structure is defined, this structure improves the heatproof of membrane material after monomer polymerization and after sol gel reaction
Property, acid and alkali-resistance and organic solvent-borne, two kinds of monomers make membrane material even structure in molecule rank combined polymerization, have good pliable and tough
Property.
Specific embodiment
Further illustrate technical solution of the present invention below by embodiment, these embodiments are intended merely to represent in detail this
Bright technology design and its exploitativeness, are not limiting the scope of the invention, are made using the technology of the present invention design
Equivalence replacement and accommodation still within protection scope of the present invention.
Embodiment 1
(1) film liquid allotment: by methacrylic acid 2- sulphur ethyl ester (sem), γ-(methacryloxypropyl) propyl trimethoxy silicane
(kh570), n- methyl pyrrolidone (nmp), distilled water and azodiisobutyronitrile (aibn) mix according to table 1 formula, are deployed into
Homogeneous solution, prepared film liquid.
(2) film liquid absorption: using aperture be 0.45 μm, porosity be 45%, thickness be 115 μm nylon66 fiber non-woven fabrics as
Base material, base material is submerged in the film liquid that step (1) is obtained, and infiltration 30 min make it be impregnated with after fully, take out base material and by its
Being positioned in the middle of two panels polyethylene terephthalate thin film, if there is bubble between base material and thin film, rolling thin film exclusion base
Bubble between material and thin film, makes base material form complex with two panels thin film；Then complex is sandwiched between two sheet glass simultaneously
The surrounding sealing of two sheet glass is made complex be in sealing state.
(3) thermal polymerization is processed: the complex after sealing is placed under 100 c temperature conditionss, initiator initiated polymerization,
After keeping said temperature condition 3 h, remove two sheet glass and simultaneously two panels thin film is peeled off, be then placed in locating after heat at a temperature of 130 c
Manage 6 h, that is, obtain cation exchange membrane.It is dipped in 0.5 mol/l nacl solution and soak 48 h, taking-up distillation after immersion
Re-dry after water washing, drying obtains final product na type cation exchange membrane after finishing.
Take each 3 pieces by formula 1 and formula 2 production sample, the sun then producing with Japan Asia stone Co., Ltd. (astom)
Ion exchange membrane carries out contrast test, and test result is shown in Table 2, and in table 2, comparative sample is referred to as with astom cmx.
Table 1 embodiment 1 formula
| Title | sem | kh570 | nmp | h2o | aibn |
| Formula 1 | 6.6225g | 2.3938g | 4.3709g | 0.0157g | 0.0339g |
| Formula 2 | 6.6225g | 3.0777g | 4.3709g | 0.0157g | 0.0364g |
Table 2 embodiment 1 test result
| Sample ID | Resistance | Transport number |
| astom cmx | 4.38 | 0.985 |
| Formula 1 sample 1 | 2.78 | 0.969 |
| Formula 1 sample 2 | 2.58 | 0.964 |
| Formula 1 sample 3 | 1.68 | 0.972 |
| Formula 2 sample 1 | 2.87 | 0.984 |
| Formula 2 sample 2 | 3.94 | 0.980 |
| Formula 2 sample 3 | 3.84 | 0.969 |
Embodiment 2
(1) film liquid allotment: by methacrylic acid 2- sulphur ethyl ester (sem), methyl methacrylate (mma), γ-(methacryl
Oxygen) propyl trimethoxy silicane (kh570), n- methyl pyrrolidone (nmp), distilled water and azodiisobutyronitrile (aibn) according to
Table 3 formula mixes, and is deployed into homogeneous solution, prepared film liquid.
(2) film liquid absorption: using aperture be 0.45 μm, porosity be 45%, thickness be 115 μm nylon66 fiber non-woven fabrics as
Base material, base material is submerged in the film liquid that step (1) is obtained, and infiltration 30 min make it be impregnated with after fully, take out base material and by its
Being positioned in the middle of two panels polyethylene terephthalate thin film, if there is bubble between base material and thin film, rolling thin film exclusion base
Bubble between material and thin film, makes base material form complex with two panels thin film；Then complex is sandwiched between two sheet glass simultaneously
The surrounding sealing of two sheet glass is made complex be in sealing state.
(3) thermal polymerization is processed: the complex after sealing is placed under 100 c temperature conditionss, initiator initiated polymerization,
After keeping said temperature condition 3 h, remove two sheet glass and simultaneously two panels thin film is peeled off, be then placed in locating after heat at a temperature of 130 c
Manage 6 h, that is, obtain cation exchange membrane.It is dipped in 0.5 mol/l nacl solution and soak 48 h, taking-up distillation after immersion
Re-dry after water washing, drying obtains final product na type cation exchange membrane after finishing.
Take each 3 pieces of the sample producing by formula 3 and formula 4, then produce with Japan Asia stone Co., Ltd. (astom)
Cation exchange membrane carries out contrast test, and test result is shown in Table 4, and in table 4, comparative sample is referred to as with astom cmx.
Table 3 embodiment 2 formula
| sem/g | mma/g | kh570/g | h2o/g | nmp/g | aibn/g | |
| Formula 3 | 10.5960 | 0.3547 | 0 | 0 | 9.9359 | 0.0582 |
| Formula 4 | 10.5960 | 0.3547 | 4.1037 | 0.0357 | 9.9359 | 0.0582 |
Table 4 embodiment 2 test result
| Resistance | Transport number | |
| astom cmx | 4.38 | 0.985 |
| Formula 3 sample 1 | 1.82 | 0.656 |
| Formula 3 sample 2 | 1.13 | 0.664 |
| Formula 3 sample 3 | 1.75 | 0.638 |
| Formula 4 sample 1 | 3.21 | 0.937 |
| Formula 4 sample 2 | 4.55 | 0.937 |
| Formula 4 sample 3 | 3.60 | 0.942 |
Embodiment 3
(1) film liquid allotment: by styrene sulfonic acid pyridine (pyss), hydroxyethyl methylacrylate (hema), γ-(methacryl
Oxygen) propyl trimethoxy silicane (kh570), distilled water and azodiisobutyronitrile (aibn) mix according to table 5 formula, be deployed into all
Even solution, prepared film liquid.
(2) film liquid absorption: using aperture be 0.45 μm, porosity be 45%, thickness be 115 μm nylon66 fiber non-woven fabrics as
Base material, base material is submerged in the film liquid that step (1) is obtained, and infiltration 30 min make it be impregnated with after fully, take out base material and by its
Being positioned in the middle of two panels polyethylene terephthalate thin film, if there is bubble between base material and thin film, rolling thin film exclusion base
Bubble between material and thin film, makes base material form complex with two panels thin film；Then complex is sandwiched between two sheet glass simultaneously
The surrounding sealing of two sheet glass is made complex be in sealing state.
(3) thermal polymerization is processed: the complex after sealing is placed under 100 c temperature conditionss, initiator initiated polymerization,
After keeping said temperature condition 3 h, remove two sheet glass and simultaneously two panels thin film is peeled off, be then placed in locating after heat at a temperature of 130 c
Manage 6 h, that is, obtain cation exchange membrane.It is dipped in 0.5 mol/l nacl solution and soak 48 h, taking-up distillation after immersion
Re-dry after water washing, drying obtains final product na type cation exchange membrane after finishing.
Take 3 pieces of the sample producing by formula 5, the cation then producing with Japan Asia stone Co., Ltd. (astom) is handed over
Change film and carry out contrast test, test result is shown in Table 6, and in table 6, comparative sample is referred to as with astom cmx.
Table 5 embodiment 3 formula
| pyss/g | hema/g | kh570/g | h2o/g | aibn/g | |
| Formula 5 | 8.0000 | 0.5127 | 2.2402 | 0.0110 | 0.0588 |
Table 6 embodiment 3 test result
| Resistance | Transport number | |
| astom cmx | 4.38 | 0.985 |
| Formula 5 sample 1 | 4.72 | 0.971 |
| Formula 5 sample 2 | 4.83 | 0.970 |
| Formula 5 sample 3 | 3.67 | 0.970 |
Embodiment 4
(1) film liquid allotment: by MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride (tmaemc), γ-(methacryloxypropyl) propyl group
Trimethoxy silane (kh570), isopropanol (ipa), distilled water and azodiisobutyronitrile (aibn) mix according to table 7 formula, adjust
It is made into homogeneous solution, prepared film liquid.
(2) film liquid absorption: using aperture be 0.45 μm, porosity be 45%, thickness be 115 μm nylon66 fiber non-woven fabrics as
Base material, base material is submerged in the film liquid that step (1) is obtained, and infiltration 30 min make it be impregnated with after fully, take out base material and by its
Being positioned in the middle of two panels polyethylene terephthalate thin film, if there is bubble between base material and thin film, rolling thin film exclusion base
Bubble between material and thin film, makes base material form complex with two panels thin film；Then complex is sandwiched between two sheet glass simultaneously
The surrounding sealing of two sheet glass is made complex be in sealing state.
(3) thermal polymerization is processed: the complex after sealing is placed under 100 c temperature conditionss, initiator initiated polymerization,
After keeping said temperature condition 3 h, remove two sheet glass and simultaneously two panels thin film is peeled off, be then placed in locating after heat at a temperature of 130 c
Manage 6 h, that is, obtain anion exchange membrane.It is dipped in 0.5 mol/l nacl solution and soak 48 h, taking-up distillation after immersion
Re-dry after water washing, drying obtains final product cl type anion exchange membrane after finishing.
Take by 3 pieces of formula 6 production sample, the anion exchange then producing with Japan Asia stone Co., Ltd. (astom)
Film carries out contrast test, and test result is shown in Table 8, and in table 8, comparative sample is referred to as with astom amx.
Table 7 embodiment 4 formula
| tmaemc/g | kh570/g | ipa/g | h2o/g | aibn/g | |
| Formula 6 | 6.6300 | 2.5357 | 2.2914 | 0.0137 | 0.0299 |
Table 8 embodiment 4 test result
| Resistance | Transport number | |
| astom amx | 3.41 | 0.883 |
| Formula 6 sample 1 | 4.86 | 0.877 |
| Formula 6 sample 2 | 5.71 | 0.876 |
| Formula 6 sample 3 | 2.94 | 0.876 |
Embodiment 5
(1) film liquid allotment: by MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride (tmaemc), dimethylaminoethyl methacrylate
(dmaema), γ-(methacryloxypropyl) propyl trimethoxy silicane (kh570), isopropanol (ipa), distilled water and azo two
Isopropyl cyanide (aibn) mixes according to table 9 formula, is deployed into homogeneous solution, prepared film liquid.
(2) film liquid absorption: using aperture be 0.45 μm, porosity be 45%, thickness be 115 μm nylon66 fiber non-woven fabrics as
Base material, base material is submerged in the film liquid that step (1) is obtained, and infiltration 30 min make it be impregnated with after fully, take out base material and by its
Being positioned in the middle of two panels polyethylene terephthalate thin film, if there is bubble between base material and thin film, rolling thin film exclusion base
Bubble between material and thin film, makes base material form complex with two panels thin film；Then complex is sandwiched between two sheet glass simultaneously
The surrounding sealing of two sheet glass is made complex be in sealing state.
(3) thermal polymerization is processed: the complex after sealing is placed under 100 c temperature conditionss, initiator initiated polymerization,
After keeping said temperature condition 3 h, remove two sheet glass and simultaneously two panels thin film peeled off, one group without 130 c heat treatments, directly
Connect and obtain anion exchange membrane, one group, through 130 c heat treatments 6h, obtains anion exchange membrane.It is dipped into 0.5 mol/l
48 h, re-dry after taking-up distilled water wash after immersion is soaked, drying obtains final product cl type anion and hands over after finishing in nacl solution
Change film.
The sample of 130 c heat treatments of learning from else's experience and each 3 pieces without the sample of 130 c heat treatments, then sub- with Japan
The anion exchange membrane that stone Co., Ltd. (astom) produces carries out contrast test, and test result is shown in Table 10, control sample in table 10
Product are referred to as with astom amx.
Table 9 embodiment 5 formula
| tmaemc/g | dmaema/g | kh570/g | ipa/g | h2o/g | aibn/g | |
| Formula 7 | 6.6300 | 3.9829 | 5.4265 | 4.0098 | 0.0240 | 0.0321 |
Table 10 embodiment 5 test result
| Resistance | Transport number | |
| astom amx | 3.41 | 0.883 |
| Formula 7 no heat treatment sample 1 | 4.49 | 0.877 |
| Formula 7 no heat treatment sample 2 | 5.52 | 0.879 |
| Formula 7 no heat treatment sample 3 | 4.92 | 0.871 |
| Formula 7 130 c heat treatment sample 1 | 16.48 | 0.881 |
| Formula 7 130 c heat treatment sample 2 | 18.58 | 0.878 |
| Formula 7 130 c heat treatment sample 3 | 18.26 | 0.875 |
Embodiment 6
(1) film liquid allotment: press the reaction in ethanol (et) by 1- vinyl imidazole (vim) and benzyl chloride (bc) of table 11 formula first
24h, is subsequently adding γ-(methacryloxypropyl) propyl trimethoxy silicane (kh570), distilled water and azodiisobutyronitrile
(aibn), it is deployed into homogeneous solution, prepared film liquid.
(2) film liquid absorption: using porosity be 44%, thickness be 40 μm polypropylene microporous support cloth as base material, by base material
It is submerged in the film liquid that step (1) is obtained, infiltration 30 min make it be impregnated with after fully, take out base material and be placed on two panels and gather
In the middle of PETP thin film, if there is bubble between base material and thin film, roll between thin film exclusion base material and thin film
Bubble, make base material and two panels thin film form complex；Then complex is sandwiched between two sheet glass and by two sheet glass
Surrounding sealing makes complex be in sealing state.
(3) thermal polymerization is processed: the complex after sealing is placed under 100 c temperature conditionss, initiator initiated polymerization,
After keeping said temperature condition 3 h, remove two sheet glass and simultaneously two panels thin film is peeled off, be then placed in locating after heat at a temperature of 130 c
Manage 6 h, that is, obtain anion exchange membrane.It is dipped in 0.5 mol/l nacl solution and soak 48 h, taking-up distillation after immersion
Re-dry after water washing, drying obtains final product cl type anion exchange membrane after finishing.
Take 3 pieces of the sample producing by formula 8, the anion then producing with Japan Asia stone Co., Ltd. (astom) is handed over
Change film and carry out contrast test, test result is shown in Table 12, and in table 12, comparative sample is referred to as with astom amx.
Table 11 embodiment 6 formula
| vim/g | bc/g | kh570/g | et/g | h2o/g | aibn/g | |
| Formula 8 | 5.1900 | 6.9448 | 0.6735 | 1.2808 | 0.0100 | 0.0128 |
Table 12 embodiment 6 test result
| Resistance | Transport number | |
| astom amx | 3.41 | 0.883 |
| Formula 8 sample 1 | 4.30 | 0.895 |
| Formula 8 sample 2 | 4.56 | 0.892 |
| Formula 8 sample 3 | 5.09 | 0.892 |
Embodiment 7
(1) film liquid allotment: press the reaction in ethanol (et) by 1- vinyl imidazole (vim) and benzyl chloride (bc) of table 13 formula first
24h, is subsequently adding vinyltrimethoxy silane (a171), distilled water and azodiisobutyronitrile (aibn), and allotment is uniformly molten
Liquid, prepared film liquid.
(2) film liquid absorption: with aperture be 0.45 μm, porosity be 45%, thickness be 115 μm of nylon66 fiber non-woven fabrics and hole
The polypropylene microporous that gap rate is 44%, thickness is 40 μm support cloth as base material, and base material is submerged into the film liquid that step (1) is obtained
In, after infiltration 30 min make it be impregnated with fully, take out base material and be placed in two panels polyethylene terephthalate thin film
Between, if there is bubble between base material and thin film, rolling the bubble that thin film is excluded between base material and thin film, making base material thin with two panels
Film forms complex；Then complex is sandwiched between two sheet glass and so that complex is in the surrounding sealing of two sheet glass close
Envelope state.
(3) thermal polymerization is processed: the complex after sealing is placed under 100 c temperature conditionss, initiator initiated polymerization,
After keeping said temperature condition 3 h, remove two sheet glass and simultaneously two panels thin film is peeled off, be then placed in locating after heat at a temperature of 130 c
Manage 6 h, that is, obtain anion exchange membrane.It is dipped in 0.5 mol/l nacl solution and soak 48 h, taking-up distillation after immersion
Re-dry after water washing, being dried after finishing is cl type anion exchange membrane.
Take each 3 pieces of sample being nylon nonwoven fabrics and polypropylene support cloth by the base material that formula 9 produces, then sub- with Japan
The anion exchange membrane that stone Co., Ltd. (astom) produces carries out contrast test, and test result is shown in Table 14, control sample in table 14
Product are referred to as with astom amx.
Table 13 embodiment 7 formula
| vim/g | bc/g | a171/g | et/g | h2o/g | aibn/g | |
| Formula 9 | 5.1900 | 6.9448 | 0.4301 | 1.257 | 0.0098 | 0.0126 |
Table 14 embodiment 7 test result
| Resistance | Transport number | |
| astom amx | 3.41 | 0.883 |
| The sample 1 based on nylon nonwoven fabrics for the formula 9 | 8.70 | 0.890 |
| The sample 2 based on nylon nonwoven fabrics for the formula 9 | 7.69 | 0.888 |
| The sample 3 based on nylon nonwoven fabrics for the formula 9 | 9.30 | 0.890 |
| The sample 1 based on polypropylene support cloth for the formula 9 | 7.17 | 0.895 |
| The sample 2 based on polypropylene support cloth for the formula 9 | 7.40 | 0.900 |
| The sample 3 based on polypropylene support cloth for the formula 9 | 8.74 | 0.899 |
After the sample of above-described embodiment preparation carries out test comparison with prior art, its technical specification basically reaches even more than
The level of prior art, illustrates that the method for the invention has exploitativeness and larger popularizing value.
Two important parameter membrane resistances of above-described embodiment intermediate ion exchange membrane and transport number pass through membrane potential test device
Measurement, this test device is similar to books " ion-exchange membrane written by heiner strathmann
Separation processes " Fig. 3 .17 in (isbn:978-0-444-50236-0).The two ends of test device are metal
Electrode, ion exchange membrane is positioned over the centre of device, and film both sides placed ag/agcl reference electrode, ion exchange at film
Effective membrane area s of film is 7cm2.
During measurement membrane resistance, inject the nacl solution of 0.5mol/l in a device, 50ma direct current is applied by metal electrode
Electric current i, potential difference e1 of two reference electrodes when measuring potential difference e2 of two reference electrodes and placement film sample when not placing film sample.Film
The computing formula of resistance r is as follows:
During measurement transport number, the solution of film sample both sides is respectively the nacl solution of 0.1mol/l and 0.5 mol/l, does not apply electricity
Stream, potential difference e1 of measurement two reference electrodes.The computing formula of film transport number t is as follows:
Wherein e2 is standard electric potential difference, and r is gas constant (8.314j/k/mol), and t is the absolute temperature of solution, and f is faraday
Constant (96480c/mol), a1/a2 refers to the activity ratio of film both sides solution.
Claims (10)
1. a kind of preparation method of hydridization ion exchange membrane it is characterised in that: by the organosilicon of one or more carbon-carbon double bonds
The ion monomer of monomer and one or more carbon-carbon double bonds is dissolved in formation monomer solution in organic solvent, so that monomer solution is entered
Enter in porous polymer matrix and make in base material radical polymerization to form complex, complex promotes molten through heat treatment
Glue-gel reaction ultimately forms hydridization ion exchange membrane.
2. hydridization ion exchange membrane as claimed in claim 1 preparation method it is characterised in that described ion monomer refer to containing from
The monomer of sub- function of exchange group or the monomer containing the group that can be converted into ion exchanging function group；Described ion monomer is solid
Determine the negatively charged monomer of group, including acrylic acid, methacrylic acid, methacrylic acid 2- sulphur ethyl ester, methacrylic acid 3- sulphur
Propyl ester, 2- acrylamide-2-methyl propane sulfonic, methacrylic acid sulfonation ethylene oxidic ester, styrene sulfonate or 1- allyl oxygen
Base -2- hydroxyphenyl sulfonate, is used for preparing cation exchange membrane；Described ion monomer is the positively charged monomer of fixed group,
Including MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, 3- acrylamido propyl trimethyl ammonium chloride, vinylbenzyltrimethyl
Ammonium chloride, vinyl benzyl chloride or 1- vinyl imidazole, are used for preparing anion exchange membrane.
3. the preparation method of hydridization ion exchange membrane as claimed in claim 1 is it is characterised in that contain in described monomer solution
The neutral monomer of one or two or more kinds, described neutral monomer includes methyl methacrylate, ethyl methacrylate, methyl-prop
Olefin(e) acid propyl ester, acrylic acid methyl ester., ethyl acrylate, propyl acrylate, acrylate, 2-(Acryloyloxy)ethanol, acrylic acid hydroxyl
Propyl ester, hydroxy methyl methacrylate, hydroxyethyl methylacrylate or Hydroxypropyl methacrylate；Described neutral monomer and ion list
The mol ratio of body is 0-0.5:1.
4. the preparation method of hydridization ion exchange membrane as claimed in claim 1 is it is characterised in that contain in described monomer solution
The cross-linking agent of one or two or more kinds, described cross-linking agent refers to that molecular structure at least contains the Organic substance of two carbon-carbon double bonds, including
Ethylene glycol dimethacrylate, divinylbenzene, dimethacrylate 1,3 butylene glycol ester, diacrylate 1,3 butylene glycol
Ester, dimethacrylate 1,4- butanediol ester, diacrylate 1,4- butanediol ester, diacrylate 1,6-HD ester, three propylene
Sour pentaerythritol ester, dimethacrylate TEG ester, divinylbenzene, trimethylolpropane trimethacrylate, different Fo Er
Ketone diisocyanate, glycidyl methacrylate or trimethylol-propane trimethacrylate；Described cross-linking agent with from
The mol ratio of sub- monomer is 0-0.5:1.
5. the preparation method of hydridization ion exchange membrane as claimed in claim 1 is it is characterised in that described monomer solution contains water
Or the small molecule organic compound of hydroxyl, the small molecule organic compound of described hydroxyl include methanol, ethanol, propanol, butanol or
Isobutanol；The small molecule organic compound of described water or hydroxyl and the mass ratio of ion monomer are 0-1:1.
6. the preparation method of hydridization ion exchange membrane as claimed in claim 1 is it is characterised in that described organic silicon monomer is silicon
Alkane coupling agent, including γ-(methacryloxypropyl) propyl trimethoxy silicane, vinyl trichlorosilane, vinyl triethoxyl
Silane or vinyltrimethoxy silane and vinyl three (b- methoxy ethoxy) silane；Described organic silicon monomer and ion list
The mol ratio of body is 0.1-1:1.
7. hydridization ion exchange membrane as claimed in claim 1 preparation method it is characterised in that: described organic solvent includes
But it is not limited to n- methyl pyrrolidone, n, n- dimethylformamide, n, n- dimethyl acetylamide or dimethyl sulfoxide；Described machine is molten
Agent is 0-2:1 with the mass ratio of ion monomer.
8. hydridization ion exchange membrane as claimed in claim 1 preparation method it is characterised in that: described radical polymerization lead to
Spend being polymerized by base of the initiator initiation being added in monomer solution, or caused by heat, light, radiation, plasma or microwave
Radical polymerization.
9. hydridization ion exchange membrane as claimed in claim 8 preparation method it is characterised in that: described initiator includes peroxide
Change benzoyl, Ammonium persulfate., 2,2- azodiisobutyronitrile, 2,2- azo two (2- methyl-prop amidine) dihydrochloride, 2,2- azo two
[2- (2- imidazoline -2- base) propane] dihydrochloride, 2,2- azo two [2- (22- imidazoline -2- base) propane] or dimethyl 2,
2- azo two (2 Methylpropionic acid ester)；Described initiator is 0.005-0.1:1 with the mol ratio of ion monomer.
10. hydridization ion exchange membrane as claimed in claim 1 preparation method it is characterised in that: described porous substrate is each
Plant material non-woven fabrics or microporous filter membrane；Described heat treatment refers to heat complex, promotes the sol-gel of siloxane group
Reaction, ultimately forms hydridization ion exchange membrane.
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| CN108855214B (en) * | 2018-06-29 | 2021-01-29 | 深圳大学 | Metal catalyst and preparation method thereof |
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| CN115106067B (en) * | 2022-06-22 | 2023-08-11 | 苏州大学 | Functional macroporous organic silica gel material and preparation method and application thereof |
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